Blends that consist of TPU and polyamide

ABSTRACT

A composition contains at least a thermoplastic polyurethane (TPU-1) and a copolyamide (PA-1), prepared by polymerization of at least one lactam and of a monomer mixture (M). The monomer mixture (M) contains at least a C 32 -C 40  dimer acid as a component (B1), and at least a C 4 -C 12  diamine as a component (B2). A process can be used for preparing such compositions, and the composition can be used for producing shaped articles.

The present invention relates to a composition comprising at least onethermoplastic polyurethane (TPU-1) and a copolyamide (PA-1), prepared bypolymerizing at least one lactam, and a monomer mixture (M) comprisingat least one C32-C40 dimer acid as component (B1) and at least oneC4-C12 diamine as component (B2). The present invention further relatesto a process for producing such compositions and to the use of acomposition of the invention for production of shaped articles.

Thermoplastic polyurethanes are widely known and are used as materialsin many sectors. The properties can be adjusted within wide ranges.Typically, thermoplastic polyurethanes can be processed within aparticular temperature range. A problem in the processing is theredissociation of the urethane bond, which, in the course of processing,can lead to degradation of the thermoplastic polyurethanes and to verylow melt strengths, and hence to problems in extrusion.

Particularly hard TPUs over and above about 40 D are difficult toprocess. For processing, the semicrystalline materials firstly have tobe melted at high temperatures; secondly, the materials break down atthese high temperatures. As a result, materials can be processed onlywithin a very small temperature range. This is a problem especially whendifferent temperatures occur at the nozzle in processes for extrusion oflarge shaped articles. In that case, there may be instances where thematerial in the colder zones of the nozzle has not yet completelymelted, but is already breaking down in the hotter zones of the nozzle.

Polyamides generally have, in contrast, high melt strength and very wideprocessing ranges. Polyamides are of particular significance in industrysince they feature very good mechanical properties and especially havehigh strength and toughness, good chemical stability and high abrasionresistance. They are used, for example, for production of fishing line,climbing rope and carpet backing. Furthermore, polyamides find use forproduction of packing films and packing sheaths.

For packing films and packing sheaths, copolyamides that combinepositive properties of different polyamides are frequently also used.The prior art describes various copolyamides.

EP 0 352 562 describes films composed of copolyamides, wherein thecopolyamides have been prepared from ε-caprolactam and preferably 1 to10 parts by weight of a dimer acid and a diamine. DE 28 46 596 describesshaped articles composed of a copolyamide of caprolactam, fatty aciddimers and hexamethylenediamine. Of particular industrial interest arenylon-6 and nylon-6,6, owing to their excellent properties can be usedin many sectors. However, nylon-6 and nylon-6,6 have very high meltingtemperatures.

WO 2018/050487 A1 describes copolyamides, wherein the copolyamide hasbeen prepared by polymerizing at least one lactam (A) and a monomermixture (M). Additionally described is the production of a polymer film(P) comprising such copolyamides.

Proceeding from the prior art, it was an object of the present inventionto provide materials that have improved melt strength and hence a broadprocessing range, particularly within the hardness range from 40 to 90D. It was a further object of the present invention to provide materialsthat have improved melt strength and hence a broad processing range, andare additionally transparent.

This object is achieved in accordance with the invention by acomposition (Z-1) comprising at least

-   -   (I) a thermoplastic polyurethane (TPU-1) and    -   (II) a copolyamide (PA-1), prepared by polymerization of        -   (A) at least one lactam, and        -   (B) a monomer mixture (M) comprising the following            components:            -   (B1) at least one C32-C40 dimer acid and            -   (B2) at least one C4-C12 diamine.

It has been found that, surprisingly, copolyamide (PA-1) can be blendedwith various thermoplastic polyurethanes. The blends have excellentmechanical properties, high toughness and high melt strength. It hasalso been found that many flame retardants, including flame retardantshaving relatively low breakdown temperature, can be incorporateddirectly into a corresponding blend or else into the copolyamide (PA-1).The materials obtained have excellent mechanical properties, hightoughness and good flammability performance.

The composition (Z-1) of the invention comprises at least onethermoplastic polyurethane (TPU-1) and a copolyamide (PA-1).

Thermoplastic polyurethanes are known in principle. They are typicallyproduced by reaction of isocyanates and isocyanate-reactive compoundsand chain extenders optionally in the presence of at least one catalystand/or customary auxiliaries and/or additives. Isocyanates,isocyanate-reactive compounds and chain extenders are also referred to,individually or collectively, as formation components.

In the context of the present invention, the customarily usedisocyanates and isocyanate-reactive compounds are suitable in principle.

Isocyanate-reactive compounds that may be used in principle include allsuitable compounds known to those skilled in the art. According to theinvention, at least one diol is preferably used as isocyanate-reactivecompound. It is possible here in the context of the present invention touse any suitable diols, for example polyether diols or polyester diolsor mixtures of two or more of these.

According to the invention, the thermoplastic polyurethane (TPU-1) isprepared preferably by using a polyol composition typically comprisingat least one polyol (P1) as isocyanate-reactive compound. In the contextof the present invention, it is possible in principle to use any polyolssuitable per se, for example polyesterols, polyetherols and/orpolycarbonate diols. For example, the polyol used may have a molecularweight (Mn) in the range from 500 g/mol to 8000 g/mol, and preferably anaverage functionality with respect to isocyanates of 1.8 to 2.3,preferably 1.9 to 2.2, especially 2. The number-average molecular weightis determined to DIN 55672-1 unless stated otherwise.

The polyol (P1) used preferably has a molecular weight in the range from600 to 2000 daltons, further preferably a molecular weight in the rangefrom 750 to 5000 daltons, especially a molecular weight of about 1000daltons.

Polyesters used may be polyesters based on diacids and diols. Diols usedare preferably diols having 2 to 10 carbon atoms, for exampleethanediol, butanediol or hexanediol, especially butane-1,4-diol ormixtures thereof. Diacids used may be any known diacids, for examplelinear or branched-chain diacids having four to 12 carbon atoms ormixtures thereof.

It is further possible in the context of the present invention to usepolyether polyols, for example those based on commonly known startersubstances and customary alkylene oxides, preferably ethylene oxide,propylene oxide and/or butylene oxide, further preferably polyetherolsbased on 1,2-propylene oxide and ethylene oxide, and especiallypolyoxytetramethylene glycols. One advantage of the polyether polyols isthat they have relatively high hydrolysis stability.

Also suitable are polyetherols having a low level of unsaturation.Polyols having a low level of unsaturation in the context of thisinvention are especially understood to mean polyether alcohols having acontent of unsaturated compounds of less than 0.02 meq/g, preferablyless than 0.01 meq/g. Such polyether alcohols are usually prepared byaddition of alkylene oxide, especially ethylene oxide, propylene oxideand mixtures thereof, onto the above-described diols or triols in thepresence of highly active catalysts.

Such highly active catalysts are preferably cesium hydroxide and multimetal cyanide catalysts, also referred to as DMC catalysts. A frequentlyand preferentially used DMC catalyst is zinc hexacyanocobaltate. The DMCcatalyst can be left in the polyether alcohol after the reaction; it istypically removed, for example by sedimentation or filtration.

In addition, in the context of the present invention, it is possible touse polytetrahydrofurans, for example having an average molecular weightMn in the range from 400 to 1800 g/mol, preferably frompolytetrahydrofurans having an average molecular weight Mn in the rangefrom 600 to 1500 g/mol, more preferably from polytetrahydrofurans havingan average molecular weight Mn in the range from 750 to 1250 g/mol, forexample in the range from 900 to 1100 g/mol.

It has been found that compositions having a particularly advantageousprofile of properties are obtained especially in the case of use ofpolyols having an average molecular weight in the range from 900 to 1100g/mol. For instance, the compositions of the invention firstly have alow melting point, and secondly good low-temperature properties.

Examples of suitable polycarbonate diols include polycarbonate diolsbased on alkanediols. Suitable polycarbonate diols are strictlydifunctional OH-functional polycarbonate diols, preferably strictlydifunctional OH-functional aliphatic polycarbonate diols. Suitablepolycarbonate diols are based, for example, on butane-1,4-diol,pentane-1,5-diol or hexane-1,6-diol, especially butane-1,4-diol,pentane-1,5-diol, hexane-1,6-diol, 3-methylpentane-1,5-diol or mixturesthereof, more preferably butane-1,4-diol, pentane-1,5-diol,hexane-1,6-diol or mixtures thereof. In the context of the presentinvention, preference is given to using polycarbonate diols based onbutane-1,4-diol and hexane-1,6-diol, polycarbonate diols based onpentane-1,5-diol and hexane-1,6-diol, polycarbonate diols based onhexane-1,6-diol and mixtures of two or more of these polycarbonatediols. Suitable polycarbonate diols have, for example, an averagemolecular weight Mn in the range from 800 to 1200 g/mol.

It has been found that the use of polycarbonate diols affordscompositions suitable for those applications having good hydrolysisstability and good aging resistance. For instance, the compositions ofthe invention, when polycarbonate diols are used as polyols, as well asgood low-temperature properties, also have high hydrolysis resistanceand good aging resistance.

However, the polymer composition, in the context of the presentinvention, as well as the polyol (P1), may also comprise one or morechain extenders (KV1) and optionally (KV2) and furtherisocyanate-reactive compounds. For example, the polyol composition maycomprise further polyols having an average molecular weight Mn in therange from 800 to 1200 g/mol.

According to the invention, it is also possible to use mixtures ofdifferent chain extenders. Chain extenders (KV1) and (KV2) used may becommonly known aliphatic, araliphatic, aromatic and/or cycloaliphaticcompounds having a molecular weight, preferably average molecularweight, of 50 g/mol to 499 g/mol, preferably difunctional compounds.Preference is given, for example, to alkanediols having 2 to 10 carbonatoms in the alkylene radical, preferably butane-1,4-diol,hexane-1,6-diol and/or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-,nona- and/or decaalkylene glycols having 3 to 8 carbon atoms, furtherpreferably unbranched alkanediols, especially propane-1,3-diol,butane-1,4-diol and hexane-1,6-diol.

In a further embodiment, the present invention accordingly also relatesto a composition as described above, wherein the chain extender (KV1)and/or the chain extender (KV2) is selected from the group consisting ofethane-1,2-diol, propane-1,3-diol, butane-1,4-diol and hexane-1,6-diol,diethylene glycol, triethylene glycol, hydroquinone bis(2-hydroxyethyl)ether and bis(2-hydroxyethyl) terephthalate.

The chain extender (KV1) in the context of the present invention isfurther preferably selected from the group consisting ofethane-1,2-diol, propane-1,3-diol, butane-1,4-diol and hexane-1,6-diol.In a further embodiment, the present invention accordingly also relatesto a composition as described above, wherein the chain extender (KV1) isbutane-1,4-diol.

According to the invention, it is also possible to use further chainextenders in the polyol composition.

It is also possible in accordance with the invention to use a polyhydricalcohol, for example propanediol and/or a further diol, that has beenobtained at least partly from renewable raw materials. It is possiblehere that the polyhydric alcohol has been obtained partly or entirelyfrom renewable raw materials. According to the invention, at least oneof the polyhydric alcohols used may be obtained at least partly fromrenewable raw materials.

What is called bio-propane-1,3-diol is obtainable, for example, fromcorn and/or sugar. A further option is the conversion of glycerol wastesfrom biodiesel production. In a further preferred embodiment of theinvention, the polyhydric alcohol is propane-1,3-diol that has been atleast partly obtained from renewable raw materials.

In a further embodiment, the present invention accordingly relates to acomposition as described above, wherein the thermoplastic polyurethaneis based to an extent of at least 30% on renewable raw materials. Onesuitable method of determination is the C14 method, for example.

In the context of the present invention, the organic isocyanatescustomarily used are suitable in principle. Organic isocyanates used maybe aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanates,more preferably tri-, tetra-, penta-, hexa-, hepta- and/or octamethylenediisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene1,4-diisocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophoronediisocyanate, IPDI), 1,4- and/or 1,3-bis(isocyanatomethyl)cyclohexane(HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4- and/or2,6-diisocyanate and/or dicyclohexylmethane 4,4′-, 2,4′- and2,2′-diisocyanate, diphenylmethane 2,2′-, 2,4′- and/or 4,4′-diisocyanate(MDI), naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and/or2,6-diisocyanate (TDI), dimethyl diphenyl 3,3′-diisocyanate,1,2-diphenylethane diisocyanate and/or phenylene diisocyanate.Particular preference is given to using 4,4′-MDI only.

Accordingly, the present invention, in a further embodiment, alsorelates to a composition as described above, wherein the thermoplasticpolyurethane (TPU-1) is based on an aromatic diisocyanate.

In an alternative embodiment, the present invention, in a furtherembodiment, also relates to a composition as described above, whereinthe thermoplastic polyurethane (TPU-1) is based on an aliphaticdiisocyanate.

In a further embodiment, the present invention accordingly relates to acomposition as described above, wherein the thermoplastic polyurethaneis based on diphenylmethane 4.4′-diisocyanate.

Further suitable aliphatic isocyanates are, for example, hexamethylenediisocyanate (HDI), or 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (H12MDI).

According to the invention, particularly preferred isocyanates arehexamethylene diisocyanate (HDI), diphenylmethane 2,2′-, 2,4′- and/or4,4′-diisocyanate (MDI) and tolylene 2,4- and/or 2,6-diisocyanate (TDI),or 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (H12MDI),particular preference being given to diphenylmethane 2,2′-, 2,4′- and/or4,4′-diisocyanate (MDI), especially diphenylmethane 4,4′-diisocyanate.

As well as the isocyanate composition and the polyol composition, thethermoplastic polyurethane (TPU1) may be prepared using furthercomponents, for example suitable catalysts or auxiliaries.

In a preferred embodiment, catalysts that accelerate especially thereaction between the NCO groups of the diisocyanates and the hydroxylgroups of the isocyanate-reactive compound and the chain extender aretertiary amines, especially triethylamine, dimethylcyclohexylamine,N-methylmorpholine, N,N′-dimethylpiperazine,2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane; in anotherpreferred embodiment, these are organic metal compounds such as titanateesters, iron compounds, preferably iron(III) acetylacetonate, tincompounds, preferably tin diacetate, tin dioctoate, tin dilaurate or thedialkyltin salts of aliphatic carboxylic acids, preferably dibutyltindiacetate, dibutyltin dilaurate, or bismuth salts in which bismuth ispreferably in oxidation states 2 or 3, especially 3. Salts of carboxylicacids are preferred. Carboxylic acids used are preferably carboxylicacids having 6 to 14 carbon atoms, more preferably having 8 to 12 carbonatoms. Examples of suitable bismuth salts are bismuth(III) neodecanoate,bismuth 2-ethylhexanoate and bismuth octanoate.

The catalysts are preferably used in amounts of 0.0001 to 0.1 parts byweight per 100 parts by weight of the isocyanate-reactive compound.Preference is given to using tin catalysts, especially tin dioctoate.

In addition to catalysts it is also possible to add customaryauxiliaries. Examples include surface-active substances, fillers,further flame retardants, nucleation agents, oxidation stabilizers,lubrication and demolding aids, dyes and pigments, optionallystabilizers, for example against hydrolysis, light, heat ordiscoloration, inorganic and/or organic fillers, reinforcers andplasticizers. Suitable auxiliary and additive substances may be foundfor example in Kunststoffhandbuch, volume VII, edited by Vieweg andHöchtlen, Carl Hanser Verlag, Munich 1966 (p. 103-113).

Production processes suitable for thermoplastic polyurethanes aredisclosed for example in EP 0 922 552 A1. DE 101 03 424 A1 or WO2006/072461 A1. Production is typically effected on a belt apparatus orin a reactive extruder, but can also be effected on the laboratoryscale, for example in a manual casting method. Depending on the physicalproperties of the components these are all mixed with one anotherdirectly or individual components are premixed and/or prereacted, forexample to give prepolymers, and only then subjected to polyaddition. Ina further embodiment a thermoplastic polyurethane is first produced fromthe building block components, optionally together with catalyst, intowhich auxiliaries may optionally also be incorporated. In that case, atleast one filler is introduced into this material and distributedhomogeneously. Homogeneous distribution is preferably effected in anextruder, preferably in a twin-screw extruder. According to theinvention, it is preferable to add the filler in portions, for example aportion of the extruder intake and a further portion of a second dosagesite, for example a side feeder. The hardness of the TPUs can be setwithin relatively broad molar ratios by varying the amounts of theformation components used, typically with rising hardness as the contentof chain extender increases.

According to the invention, the mixing ratio of the components used forpreparation of the thermoplastic polyurethane may vary within wideranges. For example, the chain extenders and the polyol used may be usedin a molar mixing ratio in the range from 20:1 to 1:1, preferably in therange from 18:1 to 2:1, further preferably in the range from 17:1 to3:1, more preferably in the range from 15:1 to 4:1.

If the mixtures of different chain extenders are used, the mixing ratioof the chain extenders used may vary within wide ranges. For example,the chain extenders may be used in a molar mixing ratio KV1:KV2 in therange from 20:1 to 3:1, preferably in the range from 15:1 to 4:1,further preferably in the range from 17:1 to 3:1, more preferably in therange from 15:1 to 4:1.

The thermoplastic polyurethane used in accordance with the inventionpreferably has a hardness in the range from 70 A to 90 D determinedaccording to DIN ISO 7619-1 (Shore A hardness test (3s)), preferably inthe range from 80 A to 95 A determined according to DIN ISO 7619-1, morepreferably in the range from 80 A to 90 A determined according to DINISO 7619-1, especially preferably in the range from 85 A to 90 Adetermined according to DIN ISO 7619-1.

In a further embodiment, the present invention accordingly also relatesto a composition as described above, wherein the thermoplasticpolyurethane (TPU-1) has a Shore hardness in the range from 70 A to 90 Ddetermined according to DIN 53505.

For preparation of the thermoplastic polyurethanes of the invention, theformation components are preferably reacted in the presence of catalystsand optionally auxiliaries and/or additives in such amounts that theratio of equivalence of NCO groups in the diisocyanates to the sum totalof the hydroxyl groups in the further formation components is 0.9 to1.1:1, preferably 0.95 to 1.05:1 and especially about 0.95 to 1.00:1.

Preference is given in accordance with the invention to usingthermoplastic polyurethanes where the thermoplastic polyurethane has anaverage molecular weight (Mw) in the range from 50 000 to 500 000 Da.The upper limit for the average molecular weight (Mw) of thethermoplastic polyurethanes is generally determined by processibilityand by the spectrum of properties desired. Further preferably, thethermoplastic polyurethane has an average molecular weight (Mw) in therange from 50 000 to 250 000 Da, especially preferably in the range from50 000 to 150 000 Da.

It is also possible in accordance with the invention for the compositionto comprise two or more thermoplastic polyurethanes differing forexample in their average molecular weight or in their chemicalcomposition. For example, the composition of the invention may comprisea first thermoplastic polyurethane TPU-1 and a second thermoplasticpolyurethane TPU-2, for example a thermoplastic polyurethane TPU-1 basedon an aliphatic diisocyanate and a further TPU-2 based on an aromaticdiisocyanate.

TPU-1 is prepared here using an aliphatic isocyanate, and TPU-2 using anaromatic isocyanate.

Organic isocyanates used to prepare the TPU-1 are preferably aliphaticor cycloaliphatic isocyanates, more preferably tri-, tetra-, penta-,hexa-, hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene1,5-diisocyanate, butylene 1,4-diisocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophoronediisocyanate, IPDI), 1,4- and/or 1,3-bis(isocyanatomethyl)cyclohexane(HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2.4- and/or2,6-diisocyanate and/or dicyclohexylmethane 4,4′-, 2,4′- and2,2′-diisocyanate.

In a further embodiment, the present invention therefore relates to acomposition as described above, wherein the thermoplastic polyurethaneTPU-1 is based on at least one aliphatic diisocyanate selected from thegroup consisting of hexamethylene diisocyanate anddi(isocyanatocyclohexyl)methane.

Organic isocyanates (a) used for the preparation of TPU-2 are preferablyaraliphatic and/or aromatic isocyanates, more preferably diphenylmethane2,2′-, 2,4′- and/or 4,4′-diisocyanate (MDI), naphthylene1,5-diisocyanate (NDI), tolylene 2.4- and/or 2,6-diisocyanate (TDI),dimethyl diphenyl 3,3′-diisocyanate, 1,2-diphenylethane diisocyanateand/or phenylene diisocyanate. Particular preference is given to using4,4′-MDI.

In a further embodiment, the present invention therefore relates to acomposition as described above, wherein the thermoplastic polyurethaneTPU-2 is based on diphenylmethane diisocyanate (MDI).

Isocyanate-reactive compounds used with preference for TPU-1 and TPU-2are a polycarbonate diol or a polytetrahydrofuran polyol. Suitablepolytetrahydrofuran polyols have, for example, a molecular weight in therange from 500 to 5000, preferably 500 to 2000, more preferably 800 to1200.

According to the invention, TPU-1 and TPU-2 are prepared preferably byusing at least one polycarbonate diol, preferably an aliphaticpolycarbonate diol. Examples of suitable polycarbonate diols includepolycarbonate diols based on alkanediols. Suitable polycarbonate diolsare strictly difunctional OH-functional polycarbonate diols, preferablystrictly difunctional OH-functional aliphatic polycarbonate diols.Suitable polycarbonate diols are based, for example, on butanediol,pentanediol or hexanediol, especially butane-1,4-diol, pentane-1,5-diol,hexane-1,6-diol, 3-methylpentane-1,5-diol or mixtures thereof, morepreferably butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol ormixtures thereof. Preference is given in the context of the presentinvention to using polycarbonate diols based on butanediol andhexanediol, polycarbonate diols based on pentanediol and hexanediol,polycarbonate diols based on hexanediol and mixtures of two or more ofthese polycarbonate diols.

It is preferable when the polycarbonate diols used for preparation ofTPU-1 and TPU-2 have a number-average molecular weight Mn in the rangefrom 500 to 4000 determined by GPC, preferably in the range from 650 to3500 determined by GPC, more preferably in the range from 800 to 3000determined by GPC.

Chain extenders which may be used for preparation of TPU-1 and TPU-2preferably include aliphatic, araliphatic, aromatic and/orcycloaliphatic compounds having a molecular weight of 0.05 kg/mol to0.499 kg/mol, preferably difunctional compounds, for example diaminesand/or alkanediols having 2 to 10 carbon atoms in the alkylene radical,di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and/ordecaalkylene glycols having 3 to 8 carbon atoms, especially 1,2-ethyleneglycol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, preferablycorresponding oligo- and/or polypropylene glycols, and it is alsopossible to use mixtures of the chain extenders. The compounds (c)preferably have primary hydroxyl groups only, and very particularlypreference is given to using mixtures of butane-1,4-diol with a furtherchain extender selected from the compounds recited above, for examplemixtures comprising butane-1,4-diol and a second chain extender in amolar ratio in the range from 100:1 to 1:1, preferably in a range from95:1 to 5:1, more preferably in a range from 90:1 to 10:1.

In a further embodiment, the present invention therefore relates to acomposition as described above, wherein the thermoplastic polyurethaneis prepared using, as chain extender, a mixture of butane-1,4-diol and afurther chain extender.

According to the invention, TPU-1 preferably has a hardness in the rangefrom 85 A to 70 D determined according to DIN ISO 7619-1, preferably inthe range from 95 A to 70 D determined according to DIN ISO 7619-1, morepreferably in the range from 55 D to 65 D determined according to DINISO 7619-1.

According to the invention, TPU-2 preferably has a hardness in the rangefrom 70 A to 70 D determined according to DIN ISO 7619-1, morepreferably in the range from 80 A to 60 D determined according to DINISO 7619-1, more preferably in the range from 80 A to 90 A determinedaccording to DIN ISO 7619-1.

In a further embodiment, the present invention therefore relates to acomposition as described above, wherein the thermoplastic polyurethaneTPU-1 has a Shore hardness in the range from 85 A to 65 D determinedaccording to DIN ISO 7619-1. In a further embodiment, the presentinvention therefore relates to a composition as described above, whereinthe thermoplastic polyurethane TPU-2 has a Shore hardness in the rangefrom 70 A to 65 D determined according to DIN ISO 7619-1.

TPU-1 preferably has a molecular weight of more than 100 000 Da; TPU-2preferably has a molecular weight in the range from 150 000 to 300 000Da. The upper limit for the number-average molecular weight of thethermoplastic polyurethanes is generally determined by processibilityand also the desired spectrum of properties.

In a further embodiment, the present invention therefore relates to acomposition as described above, wherein the thermoplastic polyurethaneTPU-1 has a molecular weight in the range from 100 000 Da to 400 000 Da.In a further embodiment, the present invention therefore relates to acomposition as described above, wherein the thermoplastic polyurethaneTPU-2 has a molecular weight in the range from 150 000 Da to 300 000 Da.

The composition of the invention comprises, for example, the at leastone thermoplastic polyurethane TPU-1 and the at least one thermoplasticpolyurethane TPU-2 in a sum total amount in the range from 5% by weightto 95% by weight based on the overall composition, especially in therange from 20% by weight to 80% by weight based on the overallcomposition, preferably in the range from 25% by weight to 75% byweight, more preferably in the range from 30% by weight to 70% byweight, based in each case on the sum total of components (I) and (II).

The thermoplastic polyurethanes may be prepared batchwise orcontinuously by the known processes, for example using reactiveextruders or the belt process, by the “one-shot” process or theprepolymer process, preferably by the “one-shot” process. In theseprocesses, the components to be reacted may be mixed with one anothersuccessively or simultaneously, with immediate onset of the reaction. Inthe extruder process, the formation components are introduced into theextruder individually or as a mixture, for example reacted preferably attemperatures of 100° C. to 280° C., more preferably 140° C. to 250° C.,and the polyurethane obtained is then extruded, cooled, and pelletized.

The composition of the invention comprises the at least onethermoplastic polyurethane (TPU1) in an amount in the range from 5% byweight to 95% by weight based on the overall composition, especially inthe range from 20% by weight to 80% by weight based on the overallcomposition, preferably in the range from 25% by weight to 75% byweight, based in each case on the sum total of components (I) and (II).

Accordingly, the present invention also relates, in a furtherembodiment, to a composition as described above, wherein the proportionof the thermoplastic polyurethane (TPU-1) in the composition is in therange from 5% to 95% by weight, based on the sum total of components (I)and (II).

The sum of components (I) and (II) here adds up to 100% by weight ineach case.

In addition, the composition (Z-1) of the invention comprises at leastone copolyamide (PA-1). The proportion of the copolyamide (PA-1) in thecomposition may vary within wide ranges and is, for example, in therange from 5% by weight to 95% by weight based on the overallcomposition, especially in the range from 20% by weight to 80% by weightbased on the overall composition, preferably in the range from 25% byweight to 75% by weight, based in each case on the sum total ofcomponents (I) and (II).

Accordingly, the present invention also relates, in a furtherembodiment, to a composition as described above, wherein the proportionof the copolyamide (PA-1) in the composition is in the range from 5% to95% by weight, based on the sum total of components (I) and (II).

In the context of the present invention, “at least one copolyamide” isunderstood to mean either exactly one copolyamide or a mixture of two ormore copolyamides.

According to the invention, the copolyamide (PA-1) is obtainable bypolymerizing the components (A) at least one lactam, and (B) a monomermixture (M) comprising components (B1) at least one C32-C40 dimer acidand (B2) at least one C4-C12 diamine.

According to the invention, the ratio of components (A) and (B) used mayvary within wide ranges. Suitable copolyamides are described, forexample, in WO 2018/050487 A1. The copolyamide (PA-1) is preferablyobtainable by polymerizing the following components:

(A) 15% to 84% by weight of at least one lactam,(B) 16% to 85% by weight of a monomer mixture (M) comprising thefollowing components:(B1) at least one C32-C40 dimer acid and(B2) at least one C4-C12 diamine,

where the percentages by weight of components (A) and (B) are each basedon the sum total of the percentages by weight of components (A) and (B).

In the context of the present invention, the terms “component (A)” and“at least one lactam” are used synonymously and therefore have the samemeaning.

The same applies to the terms “component (B)” and “a monomer mixture(M)”. These terms are likewise used synonymously in the context of thepresent invention and therefore have the same meaning.

In the context of the present invention, “at least one lactam” meanseither exactly one lactam or a mixture of two or more lactams.Preference is given to exactly one lactam.

According to the invention, the at least one copolyamide is preferablyprepared by polymerizing 15% to 84% by weight of component (A) and 16%to 85% by weight of component (B), preference being given to preparingthe copolyamide by polymerizing 40% to 83% by weight of component (A)and 17% to 60% by weight of component (B), and the at least onecopolyamide especially preferably being prepared by polymerizing 60% to80% by weight of component (A) and 20% to 40% by weight of component(B), where the percentages by weight of components (A) and (B) are eachbased on the sum total of the percentages by weight of components (A)and (B).

Preferably, the sum total of the percentages by weight of components (A)and (B) is 100% by weight.

In the context of the present invention, the percentages by weight ofcomponents (A) and (B) are based on the percentages by weight ofcomponents (A) and (B) prior to the polymerization, i.e. when components(A) and (B) have not yet reacted with one another. During thepolymerization, the weight ratio of components (A) and (B) may change ifappropriate.

According to the invention, the copolyamide is prepared by polymerizingcomponents (A) and (B). The polymerization of components (A) and (B) isknown per se to those skilled in the art. Typically, the polymerizationof components (A) and (B) is a condensation reaction. During thecondensation reaction, component (A) reacts with components (B1) and(B2) present in component (B) and if appropriate with component (B3)which is described further down and may likewise be present in component(B). This forms amide bonds between the individual components.Typically, component (A) is at least partly in open-chain form, i.e. asthe amino acid, during the polymerization.

The polymerization of components (A) and (B) can take place in thepresence of a catalyst. Suitable catalysts are all catalysts known tothose skilled in the art that catalyze the polymerization of components(A) and (B). Such catalysts are known to those skilled in the art.Preferred catalysts are phosphorus compounds, for example sodiumhypophosphite, phosphorous acid, triphenylphosphine or triphenylphosphite.

The polymerization of components (A) and (B) forms the copolyamide,which therefore gains structural units derived from component (A) andstructural units derived from component (B). Structural units derivedfrom component (B) comprise structural units derived from components(B1) and (B2) and, optionally, from component (B3).

The polymerization of components (A) and (B) forms the copolyamide as acopolymer. The copolymer may be a random copolymer but it may likewisebe a block copolymer.

In a block copolymer there is formation of blocks of units derived fromcomponent (B), and blocks of units derived from component (A). Thesealternate. In a random copolymer, there is alternation of structuralunits derived from component (A) with structural units derived fromcomponent (B). This alternation takes place randomly; for example, twostructural units derived from component (B) may be followed by onestructural unit derived from component (A), which is followed in turn byone structural unit derived from component (B), which is then followedby a structural unit comprising three structural units derived fromcomponent (A).

The at least one copolyamide (PA-1) is preferably a random copolymer.

The present invention therefore also provides a polymer film in whichthe at least one copolyamide is a random copolymer.

The preparation of the at least one copolyamide preferably comprises thefollowing steps:

-   -   a) polymerizing components (A) and (B) to obtain at least one        first copolyamide,    -   b) pelletizing the at least one first copolyamide obtained in        step a) to obtain at least one pelletized copolyamide,    -   c) extracting the at least one pelletized copolyamide obtained        in step b) with water to obtain at least one extracted        copolyamide,    -   d) drying the at least one extracted copolyamide obtained in        step c) at a temperature (Tr) to obtain the at least one        copolyamide.

Suitable reaction conditions are described, for example, in WO2018/050487 A1.

The polymerization in step a) may take place in any reactor known tothose skilled in the art. Preference is given to stirred tank reactors.It is also possible to use auxiliaries for improving reaction managementthat are known to those skilled in the art, for example defoamers suchas polydimethylsiloxane (PDMS).

In step b), the at least one first copolyamide obtained in step a) maybe pelletized by any methods known to those skilled in the art, forexample by strand pelletization or underwater pelletization.

The extraction in step c) may be effected by any methods known to thoseskilled in the art.

During the extraction in step c), by-products formed in step a) duringthe polymerization of components (A) and (B) are typically extractedfrom the at least one pelletized copolyamide.

In step d), the at least one extracted copolyamide obtained in step c)is dried. Processes for drying are known to those skilled in the art.According to the invention, the at least one extracted copolyamide isdried at a temperature (Tr). The temperature (Tr) is preferably abovethe glass transition temperature (TG_(C)) of the at least onecopolyamide and below the melting temperature (TM_(C)) of the at leastone copolyamide.

The drying in step d) is typically effected for a period in the rangefrom 1 to 100 hours, preferably in the range from 2 to 50 hours andespecially preferably in the range from 3 to 40 hours.

The at least one copolyamide typically has a glass transitiontemperature (TG_(C)). The glass transition temperature (TG_(C)) is forexample in the range from 20 to 50° C., preferably in the range from 23to 47° C. and especially preferably in the range from 25 to 45° C.,determined according to ISO 1 1357-2: 2014.

Component (A) in the context of the present invention is at least onelactam. Lactams are known per se to those skilled in the art. Preferenceis given in accordance with the invention to lactams having 4 to 12carbon atoms.

In the context of the present invention, “lactams” are understood tomean cyclic amides having preferably 4 to 12 carbon atoms, morepreferably 5 to 8 carbon atoms, in the ring. Suitable lactams areselected for example from the group consisting of 3-aminopropanolactam(propio-3-lactam; β-lactam; β-propiolactam), 4-aminobutanolactam(butyro-4-lactam; γ-lactam; γ-butyrolactam), 5-aminopentanolactam(2-piperidinone; δ-lactam; δ-valerolactam), 6-aminohexanolactam(hexano-6-lactam; ε-lactam; ε-caprolactam), 7-aminoheptanolactam(heptano-7-lactam; ζ-lactam; ζ-heptanolactam), 8-aminooctanolactam(octano-8-lactam; η-lactam; η-octanolactam), 9-aminononanolactam(nonano-9-lactam; θ-lactam; θ-nonanolactam), 10-aminodecanolactam(decano-10-lactam; ω-decanolactam), 11-aminoundecanolactam(undecano-11-lactam; ω-undecanolactam) and 12-aminododecanolactam(dodecano-12-lactam; ω-dodecanolactam).

According to the invention, the lactams may be unsubstituted or at leastmonosubstituted. If at least monosubstituted lactams are used, thenitrogen atom and/or the ring carbon atoms thereof may bear one, two ormore substituents selected independently from the group consisting ofC5- to C10-alkyl. C5- to C6-cycloalkyl, and C5- to C10-aryl.

Suitable C5- to C10-alkyl substituents are, for example, methyl, ethyl,propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. A suitable C5- toC6-cycloalkyl substituent is, for example, cyclohexyl. Preferred C5- toC10-aryl substituents are phenyl and anthranyl.

Preference is given to using unsubstituted lactams, preference beinggiven to γ-lactam (γ-butyrolactam), δ-lactam (δ-valerolactam) andε-lactam (ε-caprolactam). Particular preference is given to δ-lactam(δ-valerolactam) and ε-lactam (ε-caprolactam), and ε-caprolactam isespecially preferred.

According to the invention, component (B) is a monomer mixture (M). Themonomer mixture (M) comprises components (B1), at least one C32-C40dimer acid, and (B2), at least one C4-C12 diamine.

In the context of the present invention, a monomer mixture (M) isunderstood to mean a mixture of two or more monomers, where at leastcomponents (B1) and (B2) are present in the monomer mixture (M).

In the context of the present invention, the terms “component (B1)” and“at least one C32-C40 dimer acid” are used synonymously and thereforehave the same meaning. The same applies to the terms “component (B2)”and “at least one C4-C12 diamine”.

These terms are likewise used synonymously in the context of the presentinvention and therefore have the same meaning.

The monomer mixture (M) comprises, for example, in the range from 45 to55 mol % of component (B1) and in the range from 45 to 55 mol % ofcomponent (B2), based in each case on the sum total of the molarpercentages of components (B1) and (B2), preferably based on the totalmolar amount of component (B).

Preferably, component (B) comprises in the range from 47 to 53 mol % ofcomponent (B1) and in the range from 47 to 53 mol % of component (B2),based in each case on the sum total of the molar percentages ofcomponents (B1) and (B2), preferably based on the total molar amount ofcomponent (B).

More preferably, component (B) comprises in the range from 49 to 51 mol% of component (B1) and in the range from 49 to 51 mol % of component(B2), based in each case on the sum total of the molar percentages ofcomponents (B1) and (B2), preferably based on the total molar amount ofcomponent (B).

The sum total of the molar percentages of components (B1) and (B2)present in component (B) typically adds up to 100 mol %.

Component (B) may also additionally comprise a component (B3), at leastone C4-C20 diacid. In the context of the present invention, the terms“component (B3)” and “at least one C4-C20 diacid” are used synonymouslyand therefore have the same meaning.

When component (B) additionally comprises component (B3), it ispreferable that component (B) comprises in the range from 25 to 54.9 mol% of component (B1), in the range from 45 to 55 mol % of component (B2)and in the range from 0.1 to 25 mol % of component (B3), based in eachcase on the total molar amount of component (B).

More preferably, component (B) in that case comprises in the range from13 to 52.9 mol % of component (B1), in the range from 47 to 53 mol % ofcomponent (B2) and in the range from 0.1 to 13 mol % of component (B3),based in each case on the total molar amount of component (B).

Further preferably, component (B) in that case comprises in the rangefrom 7 to 50.9 mol % of component (B1), in the range from 49 to 51 mol %of component (B2) and in the range from 0.1 to 7 mol % of component(B3), based in each case on the total molar amount of component (B).

When component (B) additionally comprises component (B3), the molarpercentages of components (B1), (B2) and (B3) typically add up to 100mole percent.

The monomer mixture (M) may further comprise water.

Components (B1) and (B2) and optionally (B3) of component (B) can reactwith one another to obtain amides. This reaction is known per se tothose skilled in the art. Therefore, component (B) may comprisecomponents (B1) and (B2) and optionally (B3) in fully reacted form, inpartly reacted form or in unreacted form. Preferably, component (B)comprises components (B1), (B2) and optionally (B3) in unreacted form.

In the context of the present invention, “in unreacted form” thus meansthat component (B1) is present as the at least one C32-C40 dimer acidand component (B2) as the at least one C4-C12 diamine, and component(B3), if present, as the at least one C4-C20 diacid.

If components (B1) and (B2) and any (B3) present have at least partlyreacted with one another, components (B1) and (B2) and any (B3) presentare at least partly in amide form.

According to the invention, component (B1) is at least one C32-C40 dimeracid. In the context of the present invention. “at least one C32-C40dimer acid” means either exactly one C32-C40 dimer acid or a mixture oftwo or more C32-C40 dimer acids.

Dimer acids are also referred to as dimer fatty acids. C32-C40 dimeracids are known per se to those skilled in the art and are typicallyprepared by dimerizing unsaturated fatty acids. This dimerization may becatalyzed by aluminas, for example. Suitable unsaturated fatty acids forpreparing the at least one C32-C40 dimer acid are known to those skilledin the art and are, for example, unsaturated C16 fatty acids,unsaturated C16 fatty acids and unsaturated C20 fatty acids.

Component (B1) is therefore preferably prepared proceeding fromunsaturated fatty acids selected from the group consisting ofunsaturated C16 fatty acids, unsaturated C18 fatty acids and unsaturatedC20 fatty acids, particular preference being given to the unsaturatedC18 fatty acids. An example of a suitable unsaturated C16-fatty acid ispalmitoleic acid ((9Z)-hexadeca-9-enoic acid).

Suitable unsaturated C18 fatty acids are, for example, selected from thegroup consisting of petroselinic acid ((6Z)-octadeca-6-enoic acid),oleic acid ((9Z)-octadeca-9-enoic acid), elaidic acid((9E)-octadeca-9-enoic acid), vaccenic acid ((11E)-octadeca-11-enoicacid), linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid),alpha-linolenic acid ((9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid),gamma-linolenic acid ((6Z,9Z,12Z)-octadeca-6,9,12-trienoic acid),calendulic acid ((8E,10E,12Z)-octadeca-8,10,12-trienoic acid), punicicacid ((9Z,11E,13Z)-octadeca-9,11,13-trienoic acid),

alpha-eleostearic acid ((9Z,11E,13E)-octadeca-9,11,13-trienoic acid) andbeta-eleostearic acid ((9E,11E,13E)-octadeca-9,11,13-trienoic acid).Particular preference is given to unsaturated cis fatty acids selectedfrom the group consisting of petroselinic acid ((6Z)-octadeca-6-enoicacid), oleic acid ((9Z)-octadeca-9-enoic acid), elaidic acid((9E)-octadeca-9-enoic acid), vaccenic acid ((11E)-octadeca-11-enoicacid), linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid).

Suitable unsaturated C20 fatty acids are for example selected from thegroup consisting of gadoleic acid ((9Z)-eicosa-9-enoic acid), icosenoicacid ((11Z)-eicosa-11-enoic acid), arachidonic acid((5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraenoic acid) and timnodonic acid((5Z,8Z,11Z,14Z,17Z)-eicosa-5,8,11,14,17-pentaenoic acid).

Component (B1) is especially preferably at least one C36 dimer acid.

The at least one C36-dimer acid is preferably prepared from unsaturatedcis fatty acids. The C36 dimer acid is more preferably preparedproceeding from cis fatty acids selected from the group consisting ofpetroselinic acid ((6Z)-octadeca-6-enoic acid), oleic acid((9Z)-octadeca-9-enoic acid), elaidic acid ((9E)-octadeca-9-enoic acid),

vaccenic acid ((11E)-octadeca-11-enoic acid) and linoleic acid((9Z,12Z)-octadeca-9,12-dienoic acid).

The preparation of component (B1) from unsaturated fatty acids canadditionally form trimer acids; residues of unreacted unsaturated fattyacid may also remain.

The formation of trimer acids is known to those skilled in the art.

Preferably in accordance with the invention, component (B1) comprises atmost 0.5% by weight of unreacted unsaturated fatty acid and at most 0.5%by weight of trimer acid, more preferably at most 0.2% by weight ofunreacted unsaturated fatty acid and at most 0.2% by weight of trimeracid, based in each case on the total weight of component (B1).

Dimer acids (also known as dimerized fatty acids or dimer fatty acids)thus refer generally, and especially in the context of the presentinvention, to mixtures that are prepared by oligomerization ofunsaturated fatty acids. They are preparable, for example, by catalyticdimerization of plant-derived unsaturated fatty acids, using unsaturatedC16- to C20-fatty acids in particular as starting materials. The bondformation proceeds primarily by the Diels-Alder mechanism, and results,depending on the number and position of the double bonds in the fattyacids used to prepare the dimer acids, in mixtures of primarily dimericproducts having cycloaliphatic, linear aliphatic, branched aliphatic,and also C6 aromatic hydrocarbon groups between the carboxyl groups.Depending on the mechanism and/or any subsequent hydrogenation, thealiphatic radicals may be saturated or unsaturated and the proportion ofaromatic groups may also vary. The radicals between the carboxylic acidgroups then comprise 32 to 40 carbon atoms for example. They arepreferably prepared using fatty acids having 18 carbon atoms, so thatthe dimeric product thus has 36 carbon atoms. The radicals which jointhe carboxyl groups of the dimer fatty acids preferably comprise nounsaturated bonds and no aromatic hydrocarbon radicals.

In the context of the present invention, preference is thus given tousing Cie fatty acids in the preparation. It is particularly preferableto use linolenic acid, linoleic acid and/or oleic acid.

Depending on reaction management the above-described oligomerizationaffords mixtures which comprise primarily dimeric, but also trimeric,molecules and also monomeric molecules and other by-products.Purification by distillation is customary. Commercial dimer acidsgenerally comprise at least 80% by weight of dimeric molecules, up to19% by weight of trimeric molecules, and not more than 1% by weight ofmonomeric molecules and of other by-products.

It is preferable to use dimer acids that consist to an extent of atleast 90% by weight, preferably to an extent of at least 95% by weight,most preferably to an extent of at least 98% by weight, of dimeric fattyacid molecules.

The proportions of monomeric, dimeric, and trimeric molecules and ofother by-products in the dimer acids may be determined by gaschromatography (GC), for example. The dimer acids are converted to thecorresponding methyl esters by the boron trifluoride method (cf. DIN ENISO 5509) before GC analysis and then analyzed by GC.

In the context of the present invention it is thus a fundamental featureof “dimer acids” that production thereof comprises oligomerization ofunsaturated fatty acids. This oligomerization gives rise principally, inother words to an extent preferably of at least 80% by weight, morepreferably to an extent of at least 90% by weight, even more preferablyto an extent of at least 95% by weight and more particularly to anextent of at least 98% by weight, to dimeric products. The fact that theoligomerization thus forms predominantly dimeric products comprisingexactly two fatty acid molecules justifies this designation, which is inany case commonplace. An alternative expression for the relevant term“dimer acids” is thus “mixture comprising dimerized fatty acids”.

The dimer acids to be used are obtainable as commercial products.Examples include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid0975, Radiacid 0976, and Radiacid 0977 from Oleon, Pripol 1006, Pripol1009, Pripol 1012, and Pripol 1013 from Croda, Empol 1008. Empol 1012.Empol 1061, and Empol 1062 from BASF SE, and Unidyme 10 and Unidyme TIfrom Arizona Chemical.

Component (B1) has, for example, an acid number in the range from 190 to200 mg KOH/g.

According to the invention, component (B2) is at least one C4-C12diamine. In the context of the present invention, “at least one C4-C12diamine” means either exactly one C4-C12 diamine or a mixture of two ormore C4-C12 diamines. In the context of the present compound. “C4-C12diamine” is understood to mean aliphatic and/or aromatic compoundshaving four to twelve carbon atoms and two amino groups (—NH2 groups).The aliphatic and/or aromatic compounds may be unsubstituted oradditionally at least monosubstituted. If the aliphatic and/or aromaticcompounds are additionally at least monosubstituted, they may bear one,two or more substituents that do not take part in the polymerization ofcomponents (A) and (B). Such substituents are for example alkyl orcycloalkyl substituents.

These are known per se to those skilled in the art. The at least oneC4-C12 diamine is preferably unsubstituted.

Examples of suitable components (B2) are selected from the groupconsisting of 1,4-diaminobutane (butane-1,4-diamine;tetramethylenediamine; putrescine), 1,5-diaminopentane(pentamethylenediamine; pentane-1,5-diamine; cadaverine),1,6-diaminohexane (hexamethylenediamine; hexane-1,6-diamine),1-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane,1,10-diaminodecane (decamethylenediamine), 1,11-diaminoundecane(undecamethylenediamine) and 1,12-diaminododecane(dodecamethylenediamine).

Preferably, component (B2) is selected from the group consisting oftetramethylenediamine, pentamethylenediamine, hexamethylenediamine,decamethylenediamine and dodecamethylenediamine.

According to the invention, any component (B3) present in component (B)is at least one C4-C20 diacid. In the context of the present invention,“at least one C4-C20 diacid” means either exactly one C4-C20 diacid or amixture of two or more C4-C20 diacids.

In the context of the present invention, “C4-C20 diacid” is understoodto mean aliphatic and/or aromatic compounds having two to eighteencarbon atoms and two carboxyl groups (—COOH groups). The aliphaticand/or aromatic compounds may be unsubstituted or additionally at leastmonosubstituted. If the aliphatic and/or aromatic compounds areadditionally at least monosubstituted, they may bear one, two or moresubstituents that do not take part in the polymerization of components(A) and (B). Such substituents are for example alkyl or cycloalkylsubstituents. These are known to those skilled in the art. The at leastone C4-C20 diacid is preferably unsubstituted.

Suitable components (B3) are for example selected from the groupconsisting of butanedioic acid (succinic acid), pentanedioic acid(glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid(pimelic acid), octanedioic acid (suberic acid), nonanedioic acid(azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid,dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid andhexadecanedioic acid.

Preferably, component (B3) is selected from the group consisting ofpentanedioic acid (glutaric acid), hexanedioic acid (adipic acid),decanedioic acid (sebacic acid) and dodecanedioic acid.

According to the invention, the composition (Z1) can be produced, forexample, by mixing the individual components, for example thethermoplastic polyurethane (TPU1) and the polyamide (PA1), for examplein a suitable apparatus such as an extruder or a kneader. Thecomposition (Z1) can be produced here under conditions known per se.

According to the invention, it is also possible to use furtheradditives, for example flame retardants or fillers. Suitable fillers,plasticizers or flame retardants are known per se to the person skilledin the art.

In a further embodiment, the present invention accordingly relates to acomposition (Z1) as described above, wherein the composition comprisesat least one flame retardant.

In a further embodiment, the present invention also relates to acomposition (Z1) as described above, wherein the composition comprisesat least one filler.

In the context of the present invention, preference can be given tousing flame retardants selected from the group consisting of metalhydroxides, nitrogen-containing flame retardants andphosphorus-containing flame retardants. Preference is given inaccordance with the invention to flame retardants selected from thegroup consisting of melamine cyanurate, magnesium hydroxide andphosphorus-containing flame retardants.

In a further embodiment, the present invention also relates to acomposition (Z1) as described above, wherein the flame retardant isselected from the group consisting of metal hydroxides,nitrogen-containing flame retardants and phosphorus-containing flameretardants.

In a further embodiment, the present invention also further relates to acomposition as described above, wherein the composition comprises atleast one flame retardant selected from the group consisting of melamincyanurate, magnesium hydroxide and phosphorus-containing flameretardants.

Also suitable in the context of the present invention, for example, aremixtures of different flame retardants, for example mixtures comprisingone or more phosphorus-containing flame retardants.

Accordingly, the present invention, in a further embodiment, alsorelates to a composition as described above, wherein the compositioncomprises at least one first phosphorus-containing flame retardant (F1)selected from the group consisting of derivatives of phosphoric acid andderivatives of phosphonic acid, and at least one furtherphosphorus-containing flame retardant (F2) selected from the groupconsisting of derivatives of phosphinic acid.

Suitable flame retardants are, for example, also metal hydroxides. Inthe event of fire, metal hydroxides released exclusively water andtherefore do not form any toxic or corrosive smoke gas products.Furthermore, these hydroxides are capable of reducing smoke gas densityin the event of fire. However, a disadvantage of these substances isthat, in some cases, they promote the hydrolysis of thermoplasticpolyurethanes and also affect the oxidative aging of the polyurethanes.

Suitable hydroxides in the context of the present invention arepreferably those of magnesium, calcium, zinc and/or aluminum or mixturesthereof. More preferably, the metal hydroxide is selected from the groupconsisting of aluminum hydroxides, aluminum oxide hydroxides, magnesiumhydroxide and a mixture of two or more of these hydroxides.

The compositions of the invention may also comprise aphosphorus-containing flame retardant. According to the invention, it ispossible in principle to use any known phosphorus-containing flameretardants for thermoplastic polyurethanes.

Preference is given, in the context of the present invention, to usingderivatives of phosphoric acid, derivatives of phosphonic acid orderivatives of phosphinic acid or mixtures of two or more of thesederivatives. In a further preferred embodiment, thephosphorus-containing flame retardant is liquid at 21° C.

Preferably, the derivatives of phosphoric acid, phosphonic acid orphosphinic acid are salts with an organic or inorganic cation or organicesters. Organic esters are derivatives of the phosphorus-containingacids in which at least one oxygen atom bonded directly to thephosphorus has been esterified with an organic radical. In a preferredembodiment the organic ester is an alkyl ester, and in another preferredembodiment an aryl ester. More preferably, all hydroxyl groups of thecorresponding phosphorus-containing acid have been esterified.

Suitable organic phosphate esters are, for example, the triesters ofphosphoric acid, such as trialkyl phosphates and especially triarylphosphates, for example resorcinol bis(diphenyl phosphate).

Especially suitable in accordance with the invention are salts of therespective derivatives of phosphoric acid, phosphonic acid or phosphinicacid, more preferably phosphinate salts. Suitable examples in thecontext of the present invention are melamine polyphosphate ordiethylaluminum phosphinate.

In addition, it is also possible in the context of the present inventionto use nitrogen-containing flame retardants. According to the invention,it is possible in principle to use any known nitrogen-containing flameretardants for thermoplastic polyurethanes.

Suitable flame retardants in the context of the present invention are,for example, also melamine derivatives such as, in particular, melaminepolyphosphate or melamine cyanurate.

In the context of the present invention, it is also possible that thecomposition, as well as the thermoplastic polyurethane, comprisesmixtures of various flame retardants, for example a melamine derivativeand a derivative of phosphoric acid, or a melamine derivative and aderivative of phosphinic acid, or a melamine derivative, a derivative ofphosphoric acid and a derivative of phosphinic acid.

The melamine derivative may preferably be a melamine cyanurate.Accordingly, the present invention, in a further embodiment, may alsorelate to a composition comprising, as well as the thermoplasticpolyurethane, for example, a melamine cyanurate and a derivative ofphosphoric acid, or a melamine cyanurate and a derivative of phosphinicacid, or a melamine cyanurate, a derivative of phosphoric acid and aderivative of phosphinic acid. For example, the composition of theinvention comprises at least one thermoplastic polyurethane, at leastmelamine cyanurate, at least one first phosphorus-containing flameretardant (F1) selected from the group consisting of derivatives ofphosphoric acid and derivatives of phosphonic acid and at least onefurther phosphorus-containing flame retardant (F2) selected from thegroup consisting of derivatives of phosphinic acid.

Preferably, the composition, aside from the melamine cyanurate, the atleast one phosphorus-containing flame retardant (F1) and the at leastone phosphorus-containing flame retardant (F2), does not comprise anyfurther flame retardants. Further preferably, the composition of theinvention comprises melamine cyanurate, exactly onephosphorus-containing flame retardant (F1) selected from the groupconsisting of derivatives of phosphoric acid and derivatives ofphosphonic acid and exactly one phosphorus-containing flame retardant(F2) selected from the group consisting of derivatives of phosphinicacid.

Accordingly, the present invention, in a further embodiment, alsorelates to a composition as described above, wherein thephosphorus-containing flame retardant (F1) is a phosphinate.

In a further embodiment, the present invention also further relates to acomposition as described above, wherein the phosphinate is selected fromthe group consisting of aluminum phosphinates or zinc phosphinates.

In addition, the present invention, in a further embodiment, alsorelates to a composition as described above, wherein thephosphorus-containing flame retardant (F2) is a phosphoric ester.

In a further embodiment, the present invention also relates to acomposition as described above, wherein the flame retardant (F1) isselected from the group consisting of resorcinol bis(diphenyl phosphate)(RDP), bisphenol A bis(diphenyl phosphate) (BDP) and diphenyl cresylphosphate (DPK).

The proportion of the flame retardant (F) in the composition is, forexample, in the range from 2.5% to 40% by weight, based on the overallcomposition, preferably in the range from 5% to 30% by weight, based onthe overall composition, more preferably in the range from 10% to 20% byweight, based on the overall composition.

In a further embodiment, the present invention accordingly also relatesto a composition as described above, wherein the flame retardant (F) ispresent in an amount in the range from 2.5% to 40% by weight, based onthe overall composition.

In one embodiment, for preparation of the compositions of the invention,thermoplastic polyurethane and flame retardant are processed in onestep. In other preferred embodiments, for production of the compositionsof the invention, a reaction extruder, a belt system or other suitableapparatus is firstly used to produce a thermoplastic polyurethane,preferably in pellet form, into which at least one further flameretardant is then introduced in at least one further step, or else twoor more steps.

The mixing of the thermoplastic polyurethane with the at least one flameretardant is effected, for example, in a mixing unit which is preferablyan internal kneader or an extruder, preferably a twin-screw extruder. Inanother preferred embodiment using an extruder, the flame retardantintroduced is liquid at the temperature that exists downstream of theaddition thereof to the extruder in flow direction.

The composition of the invention may further comprise a filler (FS1).According to the invention, the chemical nature and form of the filler(FS1) may vary within wide ranges, provided that compatibility with thecomposition (Z1) is sufficient. The filler (FS1) should be chosen heresuch that the form and particle size of the filler enable sufficientmiscibility and homogeneous distribution in the composition.

Suitable fillers are for example glass fibers, glass beads, carbonfibers, aramid fibers, potassium titanate fibers, fibers ofliquid-crystal polymers, organic fibrous fillers or inorganicreinforcing materials. Organic fibrous fillers are for example cellulosefibers, hemp fibers, sisal or kenaf. Inorganic reinforcing materialsare, for example, ceramic fillers, such as aluminum nitride and boronnitride, or mineral fillers, such as asbestos, talc, wollastonite,microvit, silicates, chalk, calcined kaolins, mica and quartz flour.Preferably in accordance with the invention, the filler (FS1) isselected from the group consisting of glass fibers, carbon fibers,aramid fibers, potassium titanates fibers, fibers of liquid-crystallinepolymers, metal fibers, polyester fibers, polyamide fibers, organicfibrous fillers and inorganic fibrous fillers.

In a further embodiment, the present invention accordingly also relatesto a composition as described above, wherein the filler (FS1) isselected from the group consisting of glass fibers, carbon fibers,aramid fibers, potassium titanates fibers, fibers of liquid-crystallinepolymers, metal fibers, polyester fibers, polyamide fibers, organicfibrous fillers and inorganic fibrous fillers.

Fibrous fillers are preferred in the context of the present invention.In a further embodiment, the present invention accordingly also relatesto a composition as described above, wherein the filler (FS1) isfibrous.

The dimensions of the fillers used may vary within customary ranges. Thefiller used preferably has a length in the range from 3 mm to 4 mm and adiameter in the range from 1 μm to 20 μm, each determined in accordancewith ASTM D578-98. In a further embodiment, the present inventionaccordingly also relates to a composition as described above, whereinthe filler (FS1) has a length in the range from 3 mm to 4 mm and adiameter in the range from 1 μm to 20 μm, each determined in accordancewith ASTM D578-98.

The fillers, for example the fibrous fillers, may have been pretreatedfor better compatibility with the thermoplastic, for example with asilane compound.

Preference is given to using inorganic fibrous fillers. When usinginorganic fibrous fillers, a greater reinforcing effect and a higherheat resistance are observed.

According to the invention, the composition may also comprise two ormore fillers.

The proportion of the filler (FS1) in the composition is, for example,in the range from 40% to 60% by weight, based on the overallcomposition, preferably in the range from 45% to 55% by weight, based onthe overall composition, more preferably in the range from 48% to 52% byweight, based on the overall composition.

In a further embodiment, the present invention accordingly also relatesto a composition as described above, wherein the filler (FS1) is presentin an amount in the range from 40% to 60% by weight, based on theoverall composition.

According to the invention, the composition may comprise furthercomponents, for example demolding aids, UV protection, antioxidant orcolor pigments.

In a further aspect, the present invention also relates to a process forproducing a composition (Z-1). The present invention relates to aprocess for producing a composition (Z-1), comprising the followingsteps:

-   -   (a) providing        -   (I) a thermoplastic polyurethane (TPU-1) and        -   (II) a copolyamide (PA-1), prepared by polymerizing at least            one lactam, and a monomer mixture (M) comprising components            (B1) at least one C32-C40 dimer acid and (B2) at least one            C4-C12 diamine, and    -   (b) mixing components (I) and (II).

This process of the invention comprises at least steps (a) and (b). Theprocess may comprise further steps, for example drying steps ortemperature adjustments. According to the invention, it is also possibleto add further components, for example the aforementioned auxiliariesand additives.

In a further aspect, the present invention accordingly relates to aprocess as described above, wherein the components used are dried, forexample at a temperature in the range from 80 to 100° C. For example,the drying can be effected at a temperature in the range from 80 to 100°C. for a period of 2 to 4 hours.

According to the invention, in step (b), the copolyamide (PA-1) and thethermoplastic polyurethane (TPU-1) are mixed. This can be effected inapparatuses known per se to the person skilled in the art, for examplein an extruder. Suitable extruders and process conditions are known perse to the person skilled in the art. For example, the mixing in anextruder can be effected at a temperature in the range from 180 to 240°C., preferably at a temperature in the range from 190° C. to 230° C.,more preferably at a temperature in the range from 200° C. to 225° C.

Suitable dwell times in the extruder are, for example, in the range from5 to 20 minutes, preferably 10 to 15 minutes.

With regard to the preferred embodiments, reference is made to the abovedetails of the components used with preference.

Suitable processes for producing the composition are known per se to theperson skilled in the art. In the context of the present invention,processes known per se are typically used for compounding.

For example, the composition can be produced in an extruder in a mannerknown per se, for example in a twin-screw extruder. According to theinvention, it is preferable to add the filler in portions, for example aportion of the extruder intake and a further portion of a second dosagesite, for example a side feeder. The temperature here is preferably inthe range from 160 to 230° C. In the context of the present invention,the extruder can be operated, for example, at a speed in the range from150 to 300 revolutions per minute.

The present invention further relates to a composition obtained orobtainable by a process of the invention.

The present invention also relates to the use of the composition (Z1) ofthe invention or of a composition obtained or obtainable by a process ofthe invention for production of a shaped article.

In a further aspect, the present invention also further relates toshaped articles comprising a composition of the invention according toor a composition obtained or obtainable by a process of the invention.

The present invention also relates to the use of the composition of theinvention comprising at least one flame-retardant thermoplasticpolyurethane as described above for production of coatings, dampingelements, bellows, films or fibers, molded articles, floors forbuildings and transport, random-laid webs, preferably seals, rollers,shoe soles, hoses, cables, cable connectors, cable sheathings, cushions,laminates, profiles, belts, saddles, foams, plug connectors, trailingcables, solar modules, automotive trim. Use for the production of cablesheathings is preferred. Production is preferably effected from pelletmaterials by injection molding, calendering, powder sintering orextrusion and/or by additional foaming of the composition of theinvention.

On account of their good mechanical properties and good thermalcharacteristics, the thermoplastic polyurethanes of the invention andthe compositions of the invention are especially suitable for productionof films, moldings, wheels/rollers, fibers, automotive trim, hoses,cable plugs, bellows, trailing cables, cable sheathings, seals, belts ordamping elements.

The present invention thus also provides films, moldings,wheels/rollers, fibers, automotive trim, hoses, cable plugs, bellows,trailing cables, cable sheathings, seals, belts or damping elementscomprising a thermoplastic polyurethane as described above or acomposition as described above.

Further embodiments of the present invention can be found in the claimsand the examples. It will be appreciated that the features of thesubject matter/process of the invention or of the uses of the inventionrecited hereinabove and elucidated hereinbelow may be used not only inthe combination specified in each case but also in other combinationswithout departing from the scope of the invention. Thus, for example,the combination of a preferred feature with a particularly preferredfeature, or of a feature not characterized further with a particularlypreferred feature etc., is also encompassed implicitly even if thiscombination is not mentioned explicitly.

Illustrative embodiments of the present invention are detailedhereinbelow, but are not intended to limit the present invention. Inparticular, the present invention also encompasses those embodimentsthat result from the dependency references and hence combinationsspecified hereinbelow.

-   1. A composition comprising at least    -   (1) a thermoplastic polyurethane (TPU-1) and    -   (II) a copolyamide (PA-1), prepared by polymerization of        -   (A) at least one lactam, and        -   (B) a monomer mixture (M) comprising the following            components:            -   (B1) at least one C32-C40 dimer acid and            -   (B2) at least one C4-C12 diamine.-   2. The composition according to embodiment 1, wherein the    thermoplastic polyurethane (TPU-1) is based on an aromatic    diisocyanate.-   3. The composition according to embodiment 2, wherein the    thermoplastic polyurethane (TPU-1) has a Shore hardness in the range    from 70 A to 85 D, determined in accordance with DIN 53505.-   4. The composition according to embodiment 1, wherein the    thermoplastic polyurethane (TPU-1) is based on an aliphatic    diisocyanate.-   5. The composition according to any of embodiments 1 to 4, wherein    the proportion of the thermoplastic polyurethane (TPU-1) in the    composition is in the range from 5% to 95% by weight, based on the    sum total of components (I) and (II).-   6. The composition according to any of embodiments 1 to 5, wherein    the proportion of the copolyamide (PA-1) in the composition is in    the range from 5% to 95% by weight, based on the sum total of    components (I) and (II).-   7. The composition according to any of embodiments 1 to 6, wherein    the composition comprises at least one flame retardant selected from    the group consisting of melamine cyanurate, magnesium hydroxide and    phosphorus-containing flame retardants.-   8. The composition according to any of embodiments 1 to 7, wherein    the composition comprises at least one first phosphorus-containing    flame retardant (F1) selected from the group consisting of    derivatives of phosphoric acid and derivatives of phosphonic acid    and at least one further phosphorus-containing flame retardant (F2)    selected from the group consisting of derivatives of phosphinic    acid.-   9. The composition according to embodiment 8, wherein the    phosphorus-containing flame retardant (F1) is a phosphinate.-   10. The composition according to embodiment 9, wherein the    phosphinate is selected from the group consisting of aluminum    phosphinates or zinc phosphinates.-   11. The composition according to any of embodiments 8 to 10, wherein    the phosphorus-containing flame retardant (F2) is a phosphoric    ester.-   12. The composition according to any of embodiments 8 to 11, wherein    the flame retardant (F1) is selected from the group consisting of    resorcinol bis(diphenyl phosphate) (RDP), bisphenol A bis(diphenyl    phosphate) (BDP) and diphenyl cresyl phosphate (DPK).-   13. A process for producing a composition (Z-1), comprising the    steps of    -   (a) providing        -   (I) a thermoplastic polyurethane (TPU-1) and        -   (II) a copolyamide (PA-1), prepared by polymerizing at least            one lactam, and a monomer mixture (M) comprising components            (B1) at least one C32-C40 dimer acid and (B2) at least one            C4-C12 diamine, and    -   (b) mixing components (I) and (II).-   14. The use of a composition according to any of embodiments 1 to 12    for production of shaped articles.-   15. A shaped article comprising a composition according to any of    embodiments 1 to 12.-   16. A shaped article comprising a composition according to any of    embodiments 14 to 20.-   17. A shaped article comprising a composition according to any of    embodiments 22 to 23.

The examples that follow serve to illustrate the invention, but are inno way limiting in respect of the subject matter of the presentinvention.

EXAMPLES 1. Starting Materials

Ultramid RX2298®: copolymer of nylon-6 and nylon-6,36 (PA 6/6.36) fromBASF SE®, sold under the Ultramid RX2298® brand name, having a viscositynumber to DIN 53727 (0.005 g/ml H₂SO₄) of 28 ml/g, an MVR (230° C./10kg) of 115 cm³/10 min, a melting temperature of 201° C. and a density of1.054 g/cm³.

Elastollan 1180 A10: TPU of Shore hardness 80 A from BASF PolyurethanesGmbH, Elastogranstrasse 60, 49448 Lemförde, based on polytetrahydrofuranpolyol (PTHF) having a molecular weight of 1000 g/mol, butane-1,4-diol,diphenylmethane 4,4′-diisocyanate.

Elastollan 1160 D12: TPU of Shore hardness 60 D from BASF PolyurethanesGmbH, Elastogranstrasse 60, 49448 Lemförde, based on polytetrahydrofuranpolyol (PTHF) having a molecular weight of 1000, butane-1,4-diol, MDI.

Elastollan 1278 D11U: TPU of Shore hardness 78 D from BASF PolyurethanesGmbH, Elastogranstrasse 60, 49448 Lemförde, based on polytetrahydrofuranpolyol (PTHF) having a molecular weight of 1000, butane-1,4-diol, MDI.

Elastollan 1283 D11U: TPU of Shore hardness 83 D from BASF PolyurethanesGmbH, Elastogranstrasse 60, 49448 Lemförde, based on polytetrahydrofuranpolyol (PTHF) having a molecular weight of 1000, butane-1,4-diol. MDI.

Elastollan 685 A10: TPU of Shore hardness 85 A from BASF PolyurethanesGmbH, Elastogranstrasse 60, 49448 Lemförde, based on butanediol adipateester, butane-1,4-diol, MDI.

Elastollan B60 D11: TPU of Shore hardness 85 A from BASF PolyurethanesGmbH, Elastogranstrasse 60, 49448 Lemförde, based on butanediol adipateester, butane-1,4-diol, MDI.

Elastollan AC85 A12: TPU of Shore hardness 60 A from BASF PolyurethanesGmbH, Elastogranstrasse 60, 49448 Lemförde, based on polyester polyol(adipic acid, butane-1,4-diol and hexane-1,6-diol) having a molecularweight of 2000, butane-1,4-diol, hexamethylene diisocyanate.

Elastollan L1160 D10N: TPU of Shore hardness 60 D from BASFPolyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, based onpolytetrahydrofuran polyol (PTHF) having a molecular weight of 1000g/mol, 1,4-butanediol, 4,4′-diisocyanatodicyclohexylmethane.

Exolit OP 1230: Aluminum diethylphosphinate, CAS #: 225789-38-8,Clariant Produkte (Deutschland) GmbH, Chemiepark Knapsack, 50351 HOrth,water content % (w/w) <0.2, average particle size (D50) 20-40 μm.

Fyrolflex RDP: Resorcinol bis(diphenyl phosphate), CAS #: 125997-21-9,Supresta Netherlands B.V., Office Park De Hoef, Hoefseweg 1, 3821 AEAmersfoort, the Netherlands, viscosity at 25° C.=700 mPas, acid number<0.1 mg KOH/g, water content % (w/w)<0.1.

Melapur MC 15 ED: Melamine cyanurate(1,3,5-triazine-2,4,6(1H,3H,5H)-trione, compound with1,3,5-triazine-2,4,6-triamine (1:1)), CAS #: 37640-57-6, BASF SE, 67056Ludwigshafen, GERMANY, particle size D99% </=50 μm, D50%<=4.5 μm, watercontent % (w/w)<0.2.

Melapur MC 200/70: Melamine polyphosphate (nitrogen content 42-44% bywt., phosphorous content 12-14% by wt.)), CAS #: 218768-84-4. BASF SE,67056 Ludwigshafen, GERMANY, particle size D99% </=70 μm, averageparticle diameter D50%<=10 μm, water content % (w/w)<0.3.

Chopvantage HP3550 EC10-3,8: Glass fibers from PPG Industries FiberGlass, Energieweg 3, 9608 PC Westerbroek, The Netherlands. E glass,filament diameter 10 μm, length 3.8 mm.

2. Production Examples

The tables that follow list compositions in which the individualconstituents are stated in parts by weight (PW). The mixtures were eachproduced with a Berstorff ZE 40 A twin-screw extruder with screw length35 D divided into 10 barrel sections. Pelletization was effected usingstandard underwater pelletization apparatus from Gala (UWG).

Density, Shore hardness, tensile strength, tear propagation resistance,abrasion and elongation at break were determined on films having athickness of 1.6 mm. The films were extruded with an Arenz single-screwextruder having a three-zone screw with a mixing section (screw ratio1:3). The films were assessed in accordance with their appearance.

UL 94V and HB flame tests were conducted either on 1.6 mm films or on 2mm injection-molded plaques.

Moduli of elasticity, impact resistances and notched impact resistanceswere determined on injection-molded test specimens. For this purpose,test specimens were produced on an Arburg 520S having a screw diameterof 30 mm.

Burst pressures were determined on hoses having an external diameter of8.0 mm and an internal diameter of 5.5 mm. The hoses were extruded witha Kuhne single-screw extruder having a three-zone screw with a mixingsection (screw ratio 1:3).

The results are summarized in the tables that follow.

2.1 Example 1

Blends produced from Elastollan 1180 A10 and Ultramid RX2298.

Example No. 1.1 1.2 1.3 Elastollan 1180A10 80 60 20 Ultramid RX 2298 2040 80 Density Density DIN EN ISO 1183-1, 1.094 1.088 1.070 [g/cm³] A:Shore A A DIN 53505 86 95 98 Shore D D DIN ISO 7619-1: 33 43 63 Tensilestrength [MPa] DIN EN ISO 527 25 14 38 Elongation at break [%] DIN ENISO 527 560 230 250 Tear propagation kN/m DIN ISO 34-1, B: 23 39 129resistance Abrasion mm³ DIN 53516 99 141 142 Modulus of elasticity [MPa]DIN EN ISO 527 18 122 1155 Appearance transparent transparenttranslucent UL 94V (1.6 mm) V2 HB HB

2.2 Example 2

Blends produced from Elastollan 1160 D10 and Ultramid RX2298.

Example No. 2.1 2.2 2.3 2.4 Elastollan 1160D10 80 60 40 20 Ultramid RX2298 20 40 60 80 Density Density DIN EN ISO 1183- 1.148 1.124 1.1031.078 [g/cm³] 1, A: Shore D D DIN ISO 7619-1: 60 65 71 71 Tensilestrength [MPa] DIN EN ISO 527 38 31 35 40 Elongation at break [%] DIN ENISO 527 370 150 70 30 Tear propagation kN/m DIN ISO 34-1, B: 145 164 184185 resistance Abrasion mm³ DIN 53516 53 83 108 120 Modulus ofelasticity [MPa] DIN EN ISO 527 306 620 988 1277 Charpy impact 23° C.[kJ/m²] DIN EN ISO 179- unbroken unbroken unbroken unbroken 1/1eU Charpyimpact −30° C. [kJ/m²] DIN EN ISO 179- unbroken unbroken unbroken 87.51: Charpy notched impact [kJ/m²] DIN EN ISO 179 108.47 119.53 10.5 18.1resistance 23° C. 1 (1eA) Charpy notched impact [kJ/m²] DIN EN ISO 17918.94 14.91 9.47 6.47 resistance −30° C. 1 (1eA) Appearance translucenttranslucent translucent translucent UL 94V (1.6 mm) V2 HB HB HB Burstpressure at [bar] 64 not not not 23° C. determined determined determinedBurst pressure at [bar] 20 not not not 70° C. determined determineddetermined Burst pressure at [bar] 20 not not not 100° C. determineddetermined determined

2.3 Example 3

Blends produced from Elastollan 1178 D11U and Ultramid RX2298.

Example No. 3.1 3.2 3.3 3.4 Elastollan 1178D11U 80 60 40 20 Ultramid RX2298 20 40 60 80 Density Density DIN EN ISO 1183- 1.167 1.140 1.1071.085 [g/cm³] 1, A: Shore A A DIN 53505 — — — — Shore D D DIN ISO7619-1: 73 74 73 76 Tensile strength [MPa] DIN EN ISO 527 33 32 37 48Elongation at break [%] DIN EN ISO 527 320 150 145 130 Tear propagationkN/m DIN ISO 34-1, B: 180 181 145 285 resistance Abrasion mm³ DIN 5351662 86 131 94 Modulus of elasticity [MPa] DIN EN ISO 527 762 1148 15651448 Charpy impact 23° C. [kJ/m²] DIN EN ISO 179- unbroken unbrokenunbroken unbroken 1: Charpy impact −30° C. [kJ/m²] DIN EN ISO 179- 88.2878.08 84.98 unbroken 1: Charpy notched impact [kJ/m²] DIN EN ISO 17920.25 14.53 7.91 9.85 resistance 23° C. 1 (1eA) Charpy notched impact[kJ/m²] DIN EN ISO 179 6.37 7.31 7.22 5.91 resistance −30° C. 1 (1eA)Appearance translucent translucent translucent translucent UL 94V (1.6mm) V2 V2 HB HB

2.4 Example 4

Blends produced from Elastollan 1183 D11U and Ultramid RX2298.

It was possible to obtain a film only for one mixture. Shore hardnesswas determined on injection moldings in this case.

Example No. 4.1 4.2 4.3 4.4 Elastollan 1183D11U 80 60 40 20 Ultramid RX2298 20 40 60 80 Density Density DIN EN ISO 1183- 1.191 1.153 1.122Blend not [g/cm³] 1, A: producible Shore A A DIN 53505 Shore D D DIN ISO7619-1: 79 72 77 Tensile strength [MPa] DIN EN ISO 527 60 not notdetermined determined Elongation at break [%] DIN EN ISO 527 20 not notdetermined determined Tear propagation kN/m DIN ISO 34-1, B: 261 not notresistance determined determined Abrasion mm³ DIN 53516 85 93 103Modulus of elasticity [MPa] DIN EN ISO 527 2008 2017 2015 Charpy impact23° C. [kJ/m²] DIN EN ISO 179- unbroken unbroken unbroken 1: Charpyimpact −30° C. [kJ/m²] DIN EN ISO 179- 66.83 174.68 32.75 1: Charpynotched impact [kJ/m²] DIN EN ISO 179 5.63 6.75 7.5 resistance 23° C. 1(1eA) Charpy notched impact [kJ/m²] DIN EN ISO 179 4.78 5.53 6.94resistance −30° C. 1 (1eA) Appearance translucent translucenttranslucent UL 94 V (1.6 mm) V2 HB HB

2.5 Example 5

Blends produced from Elastollan 685 A10 and Ultramid RX2298.

Example No. 5.1 5.2 Elastollan 685A10 80 20 Ultramid RX 2298 20 80Density Density [g/cm³] DIN EN ISO 1183-1, A: 1.174 1.086 Shore A A DIN53505 90 — Shore D D DIN ISO 7619-1: 42 70 Tensile strength [MPa] DIN ENISO 527 46 21 Elongation at break [%] DIN EN ISO 527 490 110 Tearpropagation resistance kN/m DIN ISO 34-1, B: 58 161 Abrasion mm³ DIN53516 71 116 Modulus of elasticity [MPa] DIN EN ISO 527 36 1209Appearance transparent transparent UL 94V (1.6 mm) V2 HB

2.6 Example 6

Blends produced from Elastollan B60 D11 and Ultramid RX2298.

Example No. 6.1 6.2 Elastollan B60D11 80 20 Ultramid RX 2298 20 80Density Density [g/cm³] DIN EN ISO 1183-1, A: 1.191 1.089 Shore A A DIN53505 — — Shore D D DIN ISO 7619-1: 57 74 Tensile strength [MPa] DIN ENISO 527 42 51 Elongation at break [%] DIN EN ISO 527 430 340 Tearpropagation resistance kN/m DIN ISO 34-1, B: 115 197 Abrasion mm³ DIN53516 65 102 Modulus of elasticity [MPa] DIN EN ISO 527 587 1700Appearance translucent transparent UL 94V (1.6 mm) V2 HB

2.7 Example 7

Blends produced from Elastollan AC85 A12 and Ultramid RX2298.

Example No. 7.1 7.2 7.3 7.4 Elastollan AC 85A12 80 60 40 20 Ultramid RX2298 20 40 60 80 Density Density DIN EN ISO 1183- 1.124 1.108 1.0801.079 [g/cm³] 1, A; Shore A A DIN 53505 — — — — Shore D D DIN ISO7619-1: 43 44 57 71 Tensile strength [MPa] DIN EN ISO 527 14 16 26 38Elongation at break [%] DIN EN ISO 527 490 160 110 230 Tear propagationkN/m DIN ISO 34-1, B: 44 57 125 251 resistance Abrasion mm³ DIN 53516 5162 110 101 Modulus of elasticity [MPa] DIN EN ISO 527 29 67 370 1131Charpy impact 23° C. [kJ/m²] DIN EN ISO 179- unbroken unbroken unbrokenunbroken 1: Charpy impact −30° C. [kJ/m²] DIN EN ISO 179- unbrokenunbroken unbroken unbroken 1: Charpy notched impact unbroken unbrokenunbroken 39.19 resistance 23° C. Charpy notched impact 110.35 67.88 8.076.38 resistance −30° C. Appearance opaque opaque opaque opaque UL 94V(1.6 mm) HB HB HB HB Burst pressure at [bar] 89 not not not 23° C.determined determined determined Burst pressure at [bar] 49 not not not70° C. determined determined determined Burst pressure at [bar] 40 notnot not 100° C. determined determined determined

2.8 Example 8

Blends produced from Elastollan L1160 D12 and Ultramid RX2298.

Example No. 8.1 8.2 8.3 8.4 Elastollan AC 85A12 80% 60% 40% 20% UltramidRX 2298 20% 40% 60% 80% Density Density DIN EN ISO 1183- 1.089 1.0801.076 1.069 [g/cm³] 1, A: Shore A A DIN 53505 99 99 99 99 Shore D D DINISO 7619-1: 57 62 66 72 Tensile strength [MPa] DIN EN ISO 527 41 44 3853 Elongation at break [%] DIN EN ISO 527 390 400 330 410 Tearpropagation kN/m DIN ISO 34-1, B: 133 144 179 218 resistance Abrasionmm³ DIN 53516 95 104 96 60 Modulus of elasticity [MPa] DIN EN ISO 527201 359 640 885 Appearance translucent translucent translucenttranslucent UL 94V (1.6 mm) HB HB HB HB

2.9 Example 9

Mixtures produced from Ultramid RX2298, Exolit OP 1230 and melaminecyanurate 15ED.

Example No. 9.1 9.2 Ultramid RX 2298 80 70 Melamine cyanurate MC 15ED 1020 Exolit OP 1230 10 10 Density Density [g/cm³] DIN EN ISO 1183-1, 1.1231.147 A: Shore A A DIN 53505 — — Shore D D DIN ISO 7619-1: 77 79 Tensilestrength [MPa] DIN EN ISO 527 41 36 Elongation at break [%] DIN EN ISO527 30 90 Tear propagation resistance kN/m DIN ISO 34-1, B: 177 192Abrasion mm³ DIN 53516 83 134 Modulus of elasticity [MPa] DIN EN ISO 5271374 2032 Charpy notched impact [kJ/m²] DIN EN ISO 179 4.03 notresistance 23° C. 1 (1eA) determined Charpy notched impact [kJ/m²] DINEN ISO 179 3.29 not resistance −30° C. 1 (1eA) determined Visualassessment opaque opaque UL 94 V (1.6 mm) V2 V0

2.10 Example 10

Various illustrative mixtures produced from Ultramid RX2298, AC85 A12,1160 D0, Exolit OP 1230, Fyrolflex RDP, melamine polyphosphate MC 200/70and melamine cyanurate MC 15ED.

Example No. 10.1 10.2 10.3 10.4 Ultramid RX 2298 20 20 70 20 AC 85A12 5010 60 1160D10 50 Melamine cyanurate 10 MC 15ED Exolit OP 1230 20 20 1010 Melamine 10 10 polyphosphate MC 200/70 Fyrolflex RDP 10 DensityDensity DIN EN ISO 1183- 1.142 1.125 1.124 1.107 [g/cm³] 1, A: Shore A ADIN 53505 — 97 — 99 Shore D D DIN ISO 7619-1: 69 62 75 62 Tensilestrength [MPa] DIN EN ISO 527 26 7 35 25 Elongation at break [%] DIN ENISO 527 300 70 50 330 Tear propagation kN/m DIN ISO 34-1, B: 143 90 152133 resistance Abrasion mm³ DIN 53516 129 125 109 110 Modulus ofelasticity [MPa] DIN EN ISO 527 not not 1955 not determined determineddetermined Visual assessment opaque opaque opaque opaque UL 94 V (1.6mm) V0 V2 V0 V2

2.11 Example 11

Various illustrative mixtures produced from Ultramid RX2298, AC85 A12,1160 D10, Exolit OP 1230, Fyrolflex RDP, melamine polyphosphate MC200/70 and melamine cyanurate MC 15ED.

Example No. 11.1 11.2 11.3 11.4 11.5 11.6 Ultramid RX 2298 55 60 54 6055 55 AC 85A12 5 5 5 5 5 5 Melamine cyanurate 10 10 10 20 MC 15ED ExolitOP 1230 10 20 20 20 20 10 Melamine 10 10 polyphosphate MC 200/70Fyrolflex RDP Chopvantage 20 5 10 5 10 10 HP3550 EC10-3,8 DensityDensity DIN EN ISO 1.282 1.174 1.197 1.186 1.236 1.197 [g/cm³] 1183-1,A: Tensile strength [MPa] DIN EN ISO 527 57 37 56 41 57 62 Elongation atbreak [%] DIN EN ISO 527 5 12 8 12 8 8 Modulus of elasticity [MPa] DINEN ISO 527 16726 2640 3695 2736 3818 4075 Visual assessment opaqueopaque opaque opaque opaque opaque UL 94 V (2.0 mm) V0 V0 V0 V0 V0 V0

CITED LITERATURE

-   EP 0 352 562 A1-   DE2846596 A1-   WO 2018/050487 A1-   EP 0 922 552 A1-   DE 101 03 424 A1-   WO 2006/072461 A1

1-14. (canceled) 15: A composition, comprising at least: (I) athermoplastic polyurethane (TPU-1), and (II) a copolyamide (PA-1),prepared by polymerization of (A) at least one lactam, and (B) a monomermixture (M) comprising the following components: (B1) at least oneC32-C40 dimer acid, and (B2) at least one C4-C12 diamine. 16: Thecomposition according to claim 15, wherein the thermoplasticpolyurethane (TPU-1) is based on an aromatic diisocyanate. 17: Thecomposition according to claim 16, wherein the thermoplasticpolyurethane (TPU-1) has a Shore hardness in the range from 70 A to 85D, determined in accordance with DIN
 53505. 18: The compositionaccording to claim 15, wherein the thermoplastic polyurethane (TPU-1) isbased on an aliphatic diisocyanate. 19: The composition according toclaim 15, wherein a proportion of the thermoplastic polyurethane (TPU-1)in the composition is in a range from 5% to 95% by weight, based on asum total of components (I) and (II). 20: The composition according toclaim 15, wherein a proportion of the copolyamide (PA-1) in thecomposition is in a range from 5% to 95% by weight, based on a sum totalof components (I) and (II). 21: The composition according to claim 15,wherein the composition comprises at least one flame retardant selectedfrom the group consisting of melamine cyanurate, magnesium hydroxide,and a phosphorus-containing flame retardant. 22: The compositionaccording to claim 15, wherein the composition comprises at least onefirst phosphorus-containing flame retardant (F1) selected from the groupconsisting of a derivative of phosphoric acid and a derivative ofphosphonic acid, and wherein the composition comprises at least onefurther phosphorus-containing flame retardant (F2) selected from thegroup consisting of a derivative of phosphinic acid. 23: The compositionaccording to claim 22, wherein the at least one firstphosphorus-containing flame retardant (F1) is a phosphinate. 24: Thecomposition according to claim 23, wherein the phosphinate is selectedfrom the group consisting of an aluminum phosphinate and a zincphosphinate. 25: The composition according to claim 22, wherein the atleast one further phosphorus-containing flame retardant (F2) is aphosphoric ester. 26: The composition according to claim 22, wherein theat least one first flame retardant (F1) is selected from the groupconsisting of resorcinol bis(diphenyl phosphate) (RDP), bisphenol Abis(diphenyl phosphate) (BDP), and diphenyl cresyl phosphate (DPK). 27:A process for producing a composition (Z-1), comprising: (a) providingthe following components (I) a thermoplastic polyurethane (TPU-1), and(II) a copolyamide (PA-1), prepared by polymerizing at least one lactamand a monomer mixture (M) comprising (B1) at least one C32-C40 dimeracid, and (B2) at least one C4-C12 diamine; and (b) mixing components(I) and (II). 28: A method, comprising: producing a shaped article withthe composition according to claim
 15. 29: A shaped article, comprisingthe composition according to claim 15.